JPH08157523A - Olefin polymerization catalyst - Google Patents

Abstract

PURPOSE: To obtain an olefin polymerization catalyst which has high catalyst efficiency per unit weight of the transition metal and can give a polymer having a high molecular weight and a relatively wide molecular weight distribution or a copolymer having a narrow compositional distribution by bringing four specified components into contact with each other. CONSTITUTION: This catalyst is prepared by bringing into contact with one another a compound of formula I (wherein R<1> and R<2> are each 1-24C hydrocarbon group; X<1> is halogeno; Me<1> is Ti, Zr or Hf; 0<=p<=4; 0<=q<=4 and 0<=p+q<=4), at least one metal hydride compound selected from among compounds of formulae II, III and IV (wherein R<3> , R<4> , R<5> and R<6> are each a 1-24C hydrocarbon group; Me<2> is an element of group 13 in the periodic table; Me<3> is an element of group 1, 2 or 12 in the periodic table; and z is the valence of Me<3> ), an organic cyclic compound having at least two conjugated double bonds, and a borate and/or a borne.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention can be used for polymerizing or copolymerizing olefins to produce an olefin polymer having a relatively wide molecular weight distribution, and the molecular weight distribution can be arbitrarily controlled. Catalyst that can be used. Here, the olefin polymer is a generic term for a homopolymer and a copolymer of olefins.

[0002]

BACKGROUND OF THE INVENTION A catalyst composition comprising a zirconium compound (typically a metallocene) and an aluminoxane for producing a polyolefin, particularly an ethylene polymer or an ethylene / α-olefin copolymer. It is known to use JP-A-58-19309. However, although this technique can produce an ethylene homopolymer or copolymer in a high yield, it has a drawback that the molecular weight of the produced polymer is low and that the homopolymer has a narrow molecular weight distribution. Speaking only of increasing the molecular weight of the produced polymer, the molecular weight can be increased to some extent by appropriately selecting the type of transition metal of metallocene which is one component of the catalyst composition. For example, JP-A-63-251405 proposes to use a dicyclopentadienyl hafnium compound. However, this hafnium compound is generally not only difficult to synthesize, but also has a drawback that the polymerization activity is inferior to that of the dicyclopentadienyl zirconium compound. In addition to this, even if a dicyclopentadienyl hafnium compound is used, it is not possible to widen the molecular weight distribution of the produced polymer and to narrow the composition distribution and the composition distribution of the copolymer at the same time. was there.

In the art, there is a demand for the development of an olefin polymer having a high molecular weight and a relatively wide molecular weight distribution, and in the case of a copolymer, a narrow composition distribution. The fact is that it is not possible to produce an olefin polymer that can meet the demands of the industry by using a conventional catalyst composition containing a metallocene as a catalyst component. Further, in order to obtain a polymer in high yield using the catalyst system as described above, a large amount of aluminoxane must be used as a promoter, but since aluminoxane, especially methylaluminoxane, is expensive, the cost of the catalyst is high. become. Therefore, reduction in the amount of aluminoxane used is also strongly desired in the art.

[0004]

[Means for Solving the Problems] The present inventors have made it possible to obtain an olefin polymer having desired properties with a high content even if the ratio of aluminoxane to transition metal used is low, or even if aluminoxane is not used at all. A specific catalyst system using a novel catalyst component, which can be produced in a yield and has a completely different catalyst component structure from the conventional catalyst system, was previously proposed (Japanese Patent Laid-Open No. 6-248010, etc.). The present inventors have completed the present invention through further research based on the above proposal. That is, the first olefin polymerization catalyst according to the present invention is
It is characterized by being obtained by bringing the following components (A) to (D) into contact with each other. (A) A compound represented by the general formula Me ¹ (OR ¹ ) _p R ² _q X ¹ _4-pq [wherein R ¹ and R ² are independently a hydrocarbon residue having 1 to 24 carbon atoms, X ¹ Is a halogen atom, Me ¹ is Ti, Zr or Hf
, P is 0 ≦ p ≦ 4, q is 0 ≦ q ≦ 4, and p + q is 0.
≦ p + q ≦ 4. ] (B) At least one kind of metal hydride compounds represented by the following (a) to (c) (a) Me ² H _a R ³ _3-a (b) Me ³ [Me ² H _b R ⁴ _c (OR ⁵ ) _4-bc ] _z (c)

Embedded image [In the formula, R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a carbon number of 1 to 2;
4, a hydrocarbon group of 4, Me ² is an element of Group 13 of the periodic table, Me ³ is an element of Group 1, 2 or 12 of the periodic table, z is the valence of Me ³ , a, b, c and d
Are 1 ≦ a ≦ 3, 1 ≦ b ≦ 4, 0 ≦ c ≦ 3, 0 ≦ d, respectively.
≦ 4, and 1 ≦ b + c ≦ 4. ] (C) Organic Cyclic Compound Having Two or More Conjugated Double Bonds (D) Borate and / or Borane The second olefin polymerization catalyst according to the present invention further comprises the above (A) to (D). It is characterized in that it is obtained by bringing 5 components including the following component (E) into contact with each other. (E) Modified organoaluminum compound containing Al-O-Al bond

The first and second catalysts of the present invention not only have high catalytic efficiency per transition metal, but whichever catalyst is used, the olefin polymer obtained is 1. High molecular weight, 1. 2. The molecular weight distribution is relatively wide, and the molecular weight distribution can be freely controlled. 3. When the obtained olefin polymer is a copolymer, particularly when it is an ethylene / α-olefin copolymer, the composition distribution is narrow. 4. There is little catalyst residue in the olefin polymer produced. Low melting point, 6. It has features such as excellent heat sealability. Further, when molding the polymer produced by the method of the present invention, high-speed molding is also possible in the inflation method, moldability and mouth opening property are also very good, and the molded film has transparency and It has excellent anti-blocking properties, non-stickiness, and excellent strength such as impact strength and tensile strength. Further, the second aspect of the present invention using a modified organoaluminum compound as a catalyst component
The catalyst can maintain its catalytic efficiency at a high level even if the amount of the modified organoaluminum compound used is small. In addition to these, the above-mentioned catalysts of the present invention are extremely easy to prepare and have an advantage that the catalysts can be prepared efficiently in a short time.

As the component (A) of the present invention, one or more compounds represented by the following general formula are used. General formula: Me ¹ (OR ¹ ) _p R ² _q X ¹ _{4-pq In the} formula, R ¹ and R ² are each independently a hydrocarbon having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms. Indicates a group. This includes methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, isobutyl, tert-butyl, cyclobutyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, isohexyl. Group, cyclohexyl group,
Alkyl group such as heptyl group and octyl group, vinyl group,
Alkenyl group such as allyl group, phenyl group, tolyl group,
An aryl group such as a xylyl group, a mesityl group, an indenyl group, a naphthyl group, a benzyl group, a trityl group, a phenethyl group, a styryl group, a benzhydryl group, a phenylbutyl group, a phenylpropyl group, and a neophyll group are included, Each of these hydrocarbon groups includes all structural isomers. When the component (A) has two or more hydrocarbon groups, the individual hydrocarbon groups may be the same or different. X ¹ is fluorine,
Halogen atom of iodine, chlorine or bromine, Me ¹ is Zr,
It represents Ti or Hf, and is preferably Zr. p and q
Are 0≤p≤4, 0≤q≤4, 0≤p + q≤4, and preferably 0 <p + q≤4.

Specific examples of the compound usable as the component (A) are as follows: tetramethylzirconium, tetraethylzirconium, tetrapropylzirconium, tetra-n-butylzirconium, tetrapentylzirconium, tetraphenylzirconium, tetratolylzirconium and tetrabenzyl. Zirconium, tetramethoxyzirconium, tetraethoxyzirconium, tetrapropoxyzirconium, tetrabutoxyzirconium,
Tetraphenoxy zirconium, tetratolyloxy zirconium, tetrapentyloxy zirconium, tetrabenzyloxy zirconium, tetraallyl zirconium, tetraneophyll zirconium, trimethyl monochloro zirconium, triethyl monochloro zirconium, tripropyl monochloro zirconium, tri n-butyl monochloro zirconium, tribenzyl Monochlorozirconium, dimethyldichlorozirconium, diethyldichlorozirconium, di-n-butyldichlorozirconium, dibenzyldichlorozirconium, monomethyltrichlorozirconium, monoethyltrichlorozirconium, mono-n-butyltrichlorozirconium, monobenzyltrichlorozirconium, tetrachlorozirconium, trimethoxy mono Lorozirconium, dimethoxydichlorozirconium, monomethoxytrichlorozirconium, tetraethoxyzirconium, triethoxymonochlorozirconium, diethoxydichlorozirconium, monoethoxytrichlorozirconium, tetraisopropoxyzirconium, triisopropoxymonochlorozirconium, diisopropoxydichlorozirconium, monoiso Propoxytrichlorozirconium, tetra n-butoxy zirconium, tri n-butoxy monochloro zirconium, di n-butoxy dichloro zirconium, mono n-butoxy trichloro zirconium, tetrapentoxy zirconium, tripentoxy monochloro zirconium, dipentoxy dichloro zirconium, mono pen Toxitrichlorozirconium, tetraphenoki Cyzirconium, triphenoxymonochlorozirconium, diphenoxydichlorozirconium, monophenoxytrichlorozirconium, tetratolyloxyruconium, tritolyloxymonochlorozirconium, ditolyloxydichlorozirconium, monotolyloxytrichlorozirconium, tetrabenzyloxyzirconium, tribenzyloxy Monochlorozirconium, dibenzyloxydichlorozirconium, monobenzyloxytrichlorozirconium, trimethylmonobromozirconium, triethylmonobromozirconium, tripropylmonobromozirconium, tri-n-butylmonobromozirconium, tribenzylmonobromozirconium, dimethyldibromozirconium, diethyl Dibromozirconium, di- Butyldibromozirconium, dibenzyldibromozirconium, monomethyltribromozirconium, monoethyltribromozirconium, mono-n-butyltribromozirconium, monobenzyltribromozirconium, tetrabromozirconium, trimethoxymonobromozirconium, dimethoxydibromozirconium, monomethoxy Tribromozirconium, triethoxymonobromozirconium, diethoxydibromozirconium, monoethoxytribromozirconium, triisopropoxymonobromozirconium, diisopropoxydibromozirconium, monoisopropoxytribromozirconium, tri-n-butoxymonobromozirconium, di n-butoxydibromozirconium, mono n-butoxytribromozirconium, Pentoxymonobromozirconium, dipentoxydibromozirconium, monopentoxytribromozirconium, triphenoxymonobromozirconium, diphenoxydibromozirconium, monophenoxytribromozirconium, tritolyloxymonobromozirconium, ditolyloxydibromozirconium, mono Trilyloxytribromozirconium, Tribenzyloxymonobromozirconium, Dibenzyloxydibromozirconium, Monobenzyloxytribromozirconium, Trimethylmonoiodozirconium, Triethylmonoiodozirconium, Tripropylmonoiodozirconium, Tri-n-butylmonoiodozirconium , Tribenzyl monoiodozirconium, dimethyldiiodozirconium, die Rudiiodozirconium, di-n-butyldiiodozirconium, dibenzyldiiodozirconium, monomethyltriiodozirconium, monoethyltriiodozirconium, mono-n-butyltriiodozirconium, monobenzyltriiodozirconium, tetraiodozirconium, trimethoxymono Iodozirconium, dimethoxydiiodozirconium, monomethoxytriiodozirconium, triethoxymonoiodozirconium, diethoxydiiodozirconium, monoethoxytriiodozirconium, triisopropoxymonoiodozirconium, diisopropoxydiiodozirconium, monoisopropoxytrio Iodozirconium, tri-n-butoxymonoiodozirconium, di-n-butoxydiiodozirconium, mono-n-butoxy Triiodozirconium, tripentoxymonoiodozirconium, dipentoxydiiodozirconium, monopentoxytriiodozirconium, triphenoxymonoiodozirconium, diphenoxydiiodozirconium, monophenoxytriiodozirconium, tritolyloxymonoiodozirconium, Ditryloxydiiodozirconium, monotolyloxytriiodozirconium, tribenzyloxymonoiodozirconium, dibenzyloxydiiodozirconium, monobenzyloxytriiodozirconium, tribenzylmonomethoxyzirconium, tribenzylmonoethoxyzirconium, tribenzylmono Propoxy zirconium, tribenzyl monobutoxy zirconium, tribenzyl monophenoxydil Conium, dibenzyldimethoxyzirconium, dibenzyldiethoxyzirconium, dibenzyldipropoxyzirconium, dibenzyldibutoxyzirconium, dibenzyldiphenoxyzirconium, monobenzyltrimethoxyzirconium, monobenzyltriethoxyzirconium,
Monobenzyl tripropoxy zirconium, monobenzyl tributoxy zirconium, monobenzyl triphenoxy zirconium, trineophyll monomethoxy zirconium, trineophyll monoethoxy zirconium, trineophyll monopropoxy zirconium, trineophyll monobutoxy zirconium, trineophyll mono Phenoxyzirconium, Dineofildimethoxyzirconium, Dyneofildiethoxyzirconium, Dyneofildipropoxyzirconium, Dyneofildibutoxyzirconium, Dyneofildiphenoxyzirconium, Mononeophile trimethoxyzirconium, Mononeophile triethoxyzirconium , Mononeophile tripropoxy zirconium, mononeophyll tributoxy zirconium Mono neophyl triphenoxy zirconium,

Tetramethyltitanium, tetraethyltitanium, tetrapropyltitanium, tetra-n-butyltitanium, tetrapentyltitanium, tetraphenyltitanium, tetratolyltitanium, tetrabenzyltitanium, tetramethoxytitanium, tetraethoxytitanium, tetrapropoxytitanium, tetrabutoxy Titanium, tetraphenoxytitanium, tetratolyloxytitanium, tetrapentyloxytitanium, tetrabenzyloxytitanium, tetraallyltitanium, tetraneofiltitanium, trimethylmonochlorotitanium, triethylmonochlorotitanium, tripropylmonochlorotitanium, tri-n-butylmonochlorotitanium, Tribenzyl monochlorotitanium, dimethyl Dichlorotitanium, diethyldichlorotitanium, di-n-butyldichlorotitanium, dibenzyldichlorotitanium, monomethyltrichlorotitanium, monoethyltrichlorotitanium, mono-n-butyltrichlorotitanium, monobenzyltrichlorotitanium, tetramethoxytitanium, trimethoxymonochlorotitanium, dimethoxy Dichlorotitanium, monomethoxytrichlorotitanium, tetraethoxytitanium, triethoxymonochlorotitanium, diethoxydichlorotitanium, monoethoxytrichlorotitanium, tetraisopropoxytitanium, triisopropoxymonochlorotitanium, diisopropoxydichlorotitanium, monoisopropoxytrichlorotitanium, Tetra-n-butoxytitanium, tri-n -Butoxy monochlorotitanium, di-n-butoxydichlorotitanium,
Mono-n-butoxytrichlorotitanium, tetrapentoxytitanium, tripentoxymonochlorotitanium,
Dipentoxydichlorotitanium, monopentoxytrichlorotitanium, tetraphenoxytitanium, triphenoxymonochlorotitanium, diphenoxydichlorotitanium, monophenoxytrichlorotitanium,
Tetratolyloxytitanium, tritolyloxymonochlorotitanium, ditolyloxydichlorotitanium, monotolyloxytrichlorotitanium, tetrabenzyloxytitanium, tribenzyloxymonochlorotitanium, dibenzyloxydichlorotitanium,
Monobenzyloxytrichlorotitanium, trimethylmonobromotitanium, triethylmonobromotitanium, tripropylmonobromotitanium, tri-n-butylmonobromotitanium, tribenzylmonobromotitanium, dimethyldibromotitanium, diethyldibromotitanium, din-butyldibromo Titanium, dibenzyldibromotitanium, monomethyltribromotitanium, monoethyltribromotitanium, mono-n-butyltribromotitanium, monobenzyltribromotitanium, tetrabromotitanium, trimethoxymonobromotitanium, dimethoxydibromotitanium, monomethoxytribromo Titanium, triethoxymonobromotitanium, diethoxydibromotitanium, monoethoxytribromotitanium Um, triisopropoxy mono bromo titanium, diisopropoxy dibromo titanium, mono-isopropoxy tribromo titanium, tri n-
Butoxymonobromotitanium, di-n-butoxydibromotitanium, mono-n-butoxytribromotitanium, tripentoxymonobromotitanium, dipentoxydibromotitanium, monopentoxytribromotitanium, triphenoxymonobromotitanium, diphenoxydibromotitanium , Monophenoxytribromotitanium, tritolyloxymonobromotitanium, ditolyloxydibromotitanium, monotolyloxytribromotitanium, tribenzyloxymonobromotitanium, dibenzyloxydibromotitanium, monobenzyloxytribromotitanium, trimethylmonoiodo Titanium, triethylmonoiodotitanium, tripropylmonoiodotitanium, tri-n-butylmonoiodotitanium, Berezyl monoiodotitanium, dimethyldiiodotitanium, diethyldiiodotitanium, di-n-butyldiiodotitanium, dibenzyldiiodotitanium, monomethyltriiodotitanium, monoethyltriiodotitanium, mono-n-butyltriiodotitanium, mono Benzyltriiodotitanium, tetraiodotitanium, trimethoxymonoiodotitanium, dimethoxydiiodotitanium, monomethoxytriiodotitanium, triethoxymonoiodotitanium, diethoxydiiodotitanium, monoethoxytriiodotitanium, triisopropoxymonoiodotitanium , Diisopropoxydiiodotitanium,
Monoisopropoxytriiodotitanium, tri-n-butoxymonoiodotitanium, di-n-butoxydiiodotitanium, mono-n-butoxytriiodotitanium, tripentoxymonoiodotitanium, dipentoxydiiodotitanium, monopentoxytriiodo Titanium, triphenoxymonoiodotitanium, diphenoxydiiodotitanium, monophenoxytriiodotitanium, tritolyloxymonoiodotitanium, ditolyloxydiiodotitanium, monotolyloxytriiodotitanium, tribenzyloxymonoiodotitanium, dibenzyl Oxydiiododotitanium, monobenzyloxytriiodotitanium, tribenzylmonomethoxytitanium, tribenzylmonoethoxytitanium, tribenzylmono Ropoxytitanium, tribenzylmonobutoxytitanium, tribenzylmonophenoxytitanium, dibenzyldimethoxytitanium, dibenzyldiethoxytitanium, dibenzyldipropoxytitanium, dibenzyldibutoxytitanium, dibenzyldiphenoxytitanium, monobenzyltrimethoxytitanium , Monobenzyltriethoxytitanium, monobenzyltripropoxytitanium, monobenzyltributoxytitanium, monobenzyltriphenoxytitanium, trineophyll monomethoxytitanium, trineophyll monoethoxytitanium, trineophyll monopropoxytitanium, trineophyll mono Butoxytitanium, Trineophyll monophenoxytitanium, Dineofil dimethoxytitanium , Dyneofildiethoxytitanium, Dineofildipropoxytitanium, Dineofildibutoxytitanium, Dineofildiphenoxytitanium, Mononeophile trimethoxytitanium, Mononeophyltriethoxytitanium, Mononeophile tripropoxytitanium ,
Mononeophyll tributoxytitanium, Mononeophyll triphenoxytitanium,

Tetramethyl hafnium, tetraethyl hafnium, tetrapropyl hafnium, tetra n-butyl hafnium, tetrapentyl hafnium, tetraphenyl hafnium, tetratolyl hafnium, tetrabenzyl hafnium, tetramethoxy hafnium, tetraethoxy hafnium, tetrapropoxy hafnium, tetrabushi Triiodotitanium, toxyhafnium, tetraphenoxyhafnium, tetratolyloxyhafnium, tetrapentyloxyhafnium, tetrabenzyloxyhafnium, tetraallylhafnium, tetraneophylhafnium, trimethylmonochlorohafnium, triethylmonochlorohafnium, tripropylmonochlorohafnium, trin -Butyl monochlorohafnium, tribenzyl monoc Lolohafnium, dimethyldichlorohafnium, diethyldichlorohafnium, di-n-butyldichlorohafnium, dibenzyldichlorohafnium, monomethyltrichlorohafnium, monoethyltrichlorohafnium, mono-n-butyltrichlorohafnium, monobenzyltrichlorohafnium, tetramethoxyhafnium, trimethoxy Monochlorohafnium, dimethoxydichlorohafnium, monomethoxytrichlorohafnium, tetraethoxyhafnium, triethoxymonochlorohafnium, diethoxydichlorohafnium, monoethoxytrichlorohafnium, tetraisopropoxyhafnium, triisopropoxymonochlorohafnium, diisopropoxydichlorohafnium, monoiso Propoxytrichlorohafnium, tetra n- Butoxy hafnium, tri-n- butoxy monochloro hafnium,
Di-n-butoxydichlorohafnium, mono-n-butoxytrichlorohafnium, tetrapentoxyhafnium, tripentoxymonochlorohafnium, dipentoxydichlorohafnium, monopentoxytrichlorohafnium,
Tetraphenoxyhafnium, triphenoxymonochlorohafnium, diphenoxydichlorohafnium, monophenoxytrichlorohafnium, tetratolyloxyhafnium, tritolyloxymonochlorohafnium,
Ditolyloxydichlorohafnium, monotolyloxytrichlorohafnium, tetrabenzyloxyhafnium, tribenzyloxymonochlorohafnium, dibenzyloxydichlorohafnium, monobenzyloxytrichlorohafnium, trimethylmonobromohafnium, triethylmonobromohafnium, tripropylmonobromohafnium , Tri-n-butylmonobromohafnium, tribenzylmonobromohafnium, dimethyldibromohafnium, diethyldibromohafnium, di-n-
Butyldibromohafnium, dibenzyldibromohafnium, monomethyltribromohafnium, monoethyltribromohafnium, mono-n-butyltribromohafnium, monobenzyltribromohafnium, tetrabromohafnium, trimethoxymonobromohafnium, dimethoxydibromohafnium, monomethoxy Tribromohafnium, triethoxymonobromohafnium, diethoxydibromohafnium, monoethoxytribromohafnium, triisopropoxymonobromohafnium, diisopropoxydibromohafnium, monoisopropoxytribromohafnium, tri-n-butoxymonobromohafnium, di n-butoxydibromohafnium, mono n-butoxytribromohafnium, tripentoxymonobromohafnium, dipe Toxidibromohafnium, monopentoxytribromohafnium, triphenoxymonobromohafnium, dienoxydibromohafnium, monophenoxytribromohafnium, tritolyloxymonobromohafnium, ditolyloxydibromohafnium, monotolyloxytribromohafnium, tri Benzyloxymonobromohafnium, dibenzyloxydibromohafnium, monobenzyloxytribromohafnium, trimethylmonoiodohafnium, triethylmonoiodohafnium, tripropylmonoiodohafnium, tri-n-butylmonoiodohafnium, tribenzylmonoiodohafnium, Dimethyldiiodohafnium, diethyldiiodohafnium, di-n-butyldiiodohafnium, dibenzyldiiodohafni Um, monomethyltriiodohafnium, monoethyltriiodohafnium, mono-n-butyltriiodohafnium, monobenzyltriiodohafnium, tetraiodohafnium,
Trimethoxymonoiodohafnium, dimethoxydiiodohafnium, monomethoxytriiodohafnium, triethoxymonoiodohafnium, diethoxydiiodohafnium, monoethoxytriiodohafnium, triisopropoxymonoiodohafnium, diisopropoxydiiodohafnium, mono Isopropoxytriiodohafnium, tri-n-butoxymonoiodohafnium, di
n-butoxydiiodohafnium, mono n-butoxytriiodohafnium, tripentoxymonoiodohafnium, dipentoxydiiodohafnium, monopentoxytriiodohafnium, triphenoxymonoiodohafnium, dienoxydiiodohafnium, monophenoxy Triiodohafnium, tritolyloxymonoiodohafnium, ditolyloxydiiodohafnium, monotolyloxytriiodohafnium, tribenzyloxymonoiodohafnium, dibenzyloxydiiodohafnium, monobenzyloxytriiodohafnium,
Tribenzyl monomethoxy hafnium, tribenzyl monoethoxy hafnium, tribenzyl monopropoxy hafnium, tribenzyl monobutoxy hafnium, tribenzyl monophenoxy hafnium, dibenzyl dimethoxy hafnium, dibenzyl diethoxy hafnium, dibenzyl dipropoxy hafnium, dibenzyl di Butoxyhafnium, dibenzyldiphenoxyhafnium, monobenzyltrimethoxyhafnium, monobenzyltriethoxyhafnium, monobenzyltripropoxyhafnium, monobenzyltributoxyhafnium, monobenzyltriphenoxyhafnium, trineophile monomethoxyhafnium, trineophile mono Ethoxy hafnium, Trineophyll mono Propoxy hafnium, Trineophyll mono Butoxy hafnium, tri neophyl mono phenoxy hafnium, di neophyl dimethoxy hafnium, di neophyl diethoxy hafnium, di neophyl dipropoxy hafnium, di neophyl dibutoxy hafnium, di neophyl diphenoxy hafnium,
Examples include mononeophyll trimethoxy hafnium, mononeophyll triethoxy hafnium, mononeophyll tripropoxy hafnium, mononeophyll tributoxy hafnium, and mononeophyll triphenoxy hafnium.

Among the above compounds, tetramethylzirconium, tetraethylzirconium, tetrabenzylzirconium, tetrapropoxyzirconium, tripropoxymonochlorozirconium, tetrabutoxyzirconium, tetrachlorozirconium, tetrobutoxytitanium and tetrabutoxyhafnium are among the above compounds. Tetraalkoxy zirconium such as tetrapropoxy zirconium and tetrabutoxy zirconium is particularly preferable.

As the component (B) of the present invention, at least one of the metal hydride compounds represented by the following (a) to (c) is used. (A) Me ² H _a R ³ _3-a (b) Me ³ [Me ² H _b R ⁴ _c (OR ⁵ ) _4-bc ] _z (c) Chemical _formula 4

[Chemical 4] In the above general formulas (a) to (c), Me ² is an element of Group 13 of the periodic table such as boron or aluminum, Me ^2
3 represents an element of Group 1 of the periodic table such as lithium, sodium and potassium, an element of Group 2 of the periodic table such as magnesium, calcium and barium, or an element of Group 12 of the periodic table such as zinc. R ³ , R ⁴ , R ⁵ and R ⁶ individually represent a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 6 carbon atoms, which includes methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl and isobutyl. , T-butyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, isohexyl, cyclohexyl, heptyl, octyl, decyl, dodecyl, etc. alkyl groups; vinyl, allyl, etc. alkenyl groups; phenyl, tolyl,
Each aryl group such as xylyl, mesityl, indenyl, and naphthyl; and each aralkyl group such as benzyl, trityl, phenethyl, styryl, benzhydryl, phenylbutyl, phenylpropyl, neophyl, and the like are included. When two or more hydrocarbon groups are present in one molecule, the individual hydrocarbon groups may be the same or different. z represents the valence of Me ³ , and a, b and c
Are 1 ≦ a ≦ 3, 1 ≦ b ≦ 4, 0 ≦ c ≦ 3, respectively,
Moreover, 1 ≦ b + c ≦ 4, and d is 0 ≦ d ≦ 4, preferably 0 ≦ d ≦ 2, more preferably 0 ≦ d ≦ 1, and most preferably d = 0. And a, b, c and d
Is usually an integer.

In metal hydride (b), Me
^{When 2} is boron, Me ³ is preferably lithium, sodium or zinc, and when Me ² is aluminum, Me ³ is preferably lithium, sodium or potassium. Further, in the metal hydride (c), the bonding position of the hydrocarbon group R6 is not particularly limited, but in the case of d = 2, bonding to the 4-position, 5-position, 4-position and 6-position, or 5-position and 6-position, When d = 1, it is customary to bond to the 4-position or 5-position.

Specific examples of the compound usable as the component (B) include aluminum hydride, dimethyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, diisopropyl aluminum hydride, dibutyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum. Hydride, dicyclohexyl aluminum hydride, lithium aluminum hydride, sodium aluminum hydride, lithium aluminum trimethoxy hydride,
Sodium aluminum trimethoxy hydride, lithium aluminum triethoxy hydride, sodium aluminum triethoxy hydride, lithium aluminum tri tert-butoxy hydride, sodium aluminum tri t-butoxy hydride,
Borane, diborane, 2,3-dimethyl-2-butylborane, bis (3-methyl-2-butyl) borane, dicyclohexylborane, diisopinocanphenylborane, 9-
Borabicyclo [3,3,1] nonane, catecholborane, lithium borohydride, sodium borohydride, zinc borohydride, magnesium borohydride, calcium borohydride, barium borohydride, lithium triethylborohydride, lithium triisobutylborohydride, calum Triisobutyl borohydride, sodium cyanoborohydride, potassium cyanoborohydride,
Catechol borane (1,3,2-benzodioxaboralol), 4-methyl-1,3,2-benzodioxaboralol, 5-methyl-1,3,2-benzodioxaboralol, 4, 5-dimethyl-1,3,2-benzodioxaboralol, 4,6-dimethyl-1,3,2-benzodioxaboralol, 4,7-dimethyl-1,3,2-
Benzodioxaboralol, 4-ethyl-1,3,2-
Benzodioxaboralol, 5-ethyl-1,3,2-
Benzodioxaboralol, 4,5-diethyl-1,
3,2-Benzodioxaboraole, 4,6-diethyl 1,3,2-benzodioxaboralol, 4,7-diethyl-1,3,2-benzodioxaboralol, 4-
Propyl-1,3,2-benzodioxaboralol, 5
-Propyl-1,3,2-benzodioxaboralol,
4,5-dipropyl-1,3,2-benzodioxaboralol, 4,6-dipropyl-1,3,2-benzodioxaboralol, 4,7-dipropyl-1,3,2-benzodi Oxaboralol, 4,5,6-trimethyl-
1,3,2-benzodioxaboralol, 4,5,7-
Trimethyl-1,3,2-benzodioxaboralol,
Examples include 4,5,6,7-tetramethyl-1,3,2-benzodioxaboralol. Among these, aluminum hydride, dimethyl aluminum hydride, diethyl aluminum hydride, diisobutyl aluminum hydride, lithium aluminum hydride, lithium aluminum trimethoxy hydride, sodium borohydride, lithium triisobutyl borohydride, potassium triisobutyl borohydride and the like are preferable. Each of the above compounds may be used in combination of two or more, and examples of the combination include diisobutylaluminum hydride and sodium borohydride, diisobutylaluminum hydride and lithium aluminum hydride, lithium aluminum triethoxyhydrate, and sodium borohydride. A combination of lithium aluminum triethoxy hydride and lithium aluminum hydride is preferable.

As the component (C), an organic cyclic compound having two or more conjugated double bonds is used, which has two or more conjugated double bonds, preferably 2 to 4 and more preferably 2 to. A cyclic hydrocarbon compound having one or two or more rings having three and having a total carbon number of 4 to 24, preferably 4 to 12; the cyclic hydrocarbon compound is partially a hydrocarbon group of 1 to 6 (Typically, a C1-C12 alkyl group or aralkyl group) substituted cyclic hydrocarbon compound; 2 or more, preferably 2-4, more preferably 2-3 conjugated double bonds Having a total carbon number of 4 to 24, preferably 4
An organosilicon compound having a cyclic hydrocarbon group which is ~ 12;
Organosilicon compounds in which the cyclic hydrocarbon group is partially substituted with 1 to 6 hydrocarbon residues; further, alkali metal salts (sodium salt, lithium salt, etc.) of the above compounds are included.

A particularly preferred organic cyclic compound is a compound having a cyclopentadiene structure in the molecule, a typical example of which is the compound represented by the following chemical formula 5.

Embedded image [Wherein R ⁷ , R ⁸ , R ⁹ and R ¹⁰ represent hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and when any two of these are hydrocarbon groups, these hydrocarbon groups are To form a ring having a conjugated double bond. ]

As the hydrocarbon groups R ⁷ , R ⁸ , R ⁹ and R ¹⁰ of Chemical formula 5, each alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, hexyl and octyl; aryl such as phenyl Examples thereof include alkoxy groups such as methoxy, ethoxy, and propoxy; aryloxy groups such as phenoxy; and aralkyl groups such as benzyl. Further, when any two of the hydrocarbon groups R ^{7 to} R ¹⁰ together form a ring having a conjugated double bond, the ring is usually a 6 to 8 membered ring. Specific examples of the compound represented by Chemical formula 5 include cyclopentadiene, indene, azulene, and the like, as well as alkyl derivatives, aryl derivatives, aralkyl derivatives, alkoxy derivatives and aryloxy derivatives of these compounds. Further, a compound in which two or more of the compounds represented by Chemical formula 5 are bonded (crosslinked) via an alkylene group (the carbon number thereof is usually 2 to 8, preferably 2 to 3) is also a component (C) of the present invention. Can be used.

The organosilicon compound having a cyclic hydrocarbon group can be represented by (Cp) _L SiR ¹¹ _4-L . Here, Cp represents the cyclic hydrocarbon group exemplified by cyclopentadienyl, substituted cyclopentadienyl, indenyl, and substituted indenyl, and R ¹¹
Is methyl, ethyl, propyl, isopropyl, butyl,
As exemplified by alkyl groups such as t-butyl, hexyl and octyl; alkoxy groups such as methoxy, ethoxy, propoxy and butoxy; aryl groups such as phenyl; aryloxy groups such as phenoxy; aralkyl groups such as benzyl. It represents a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 or hydrogen, and L is 1≤L≤4, preferably 1≤L≤3.

Therefore, the organic cyclic hydrocarbon compounds usable as the component (C) of the present invention include the following compounds. Cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, t-butylcyclopentadiene, hexylcyclopentadiene, octylcyclopentadiene, 1,2-dimethylcyclopentadiene, 1,3-
Dimethylcyclopentadiene, 1,2,4-trimethylcyclopentadiene, 1,2,3,4-tetramethylcyclopentadiene, pentamethylcyclopentadiene, indene, 4-methyl-1-indene, 4,7-dimethylindene, 4 7,5,6,7-Tetrahydroindene, cycloheptatriene, methylcycloheptatriene, cyclooctatetraene, methylcyclooctatetraene, azulene, methylazulene, ethylazulene, fluorene, methylfluorene having 7 to 7 carbon atoms 24 cyclopolyene or substituted cyclopolyene, monocyclopentadienylsilane, biscyclopentadienylsilane, triscyclopentadienylsilane, tetrakiscyclopentadienylsilane, monocyclopentadienylmonomethylsilane, monocyclopentadienyl Monoethylsilane, Nocyclopentadienyldimethylsilane, monocyclopentadienyldiethylsilane, monocyclopentadienyltrimethylsilane,
Monocyclopentadienyl triethylsilane, monocyclopentadienyl monomethoxysilane, monocyclopentadienyl monoethoxysilane, monocyclopentadienyl monophenoxysilane, biscyclopentadienyl monomethylsilane, dicyclopentadienyl monoethylsilane Silane, biscyclopentadienyldimethylsilane, biscyclopentadienyldiethylsilane, biscyclopentadienylmethylethylsilane, biscyclopentadienyldipropylsilane, biscyclopentadienylethylpropylsilane, biscyclopentadienyl Diphenylsilane, biscyclopentadienylphenylmethylsilane, biscyclopentadienylmonomethoxysilane, biscyclopentadienylmonoethoxysilane, triscyclopentadiene Nylmonomethylsilane, triscyclopentadienylmonoethylsilane, triscyclopentadienylmonomethoxysilane, triscyclopentadienylmonoethoxysilane, 3-methylcyclopentadienylsilane, bis3-methylcyclopentadienylsilane, 3-methylcyclopentadienylmethylsilane, 1,2-dimethylcyclopentadienylsilane,
1,3-dimethylcyclopentadienylsilane, 1,
2,4-trimethylcyclopentadienylsilane, 1,
2,3,4-tetramethylcyclopentadienylsilane, pentamethylcyclopentadienylsilane, monoindenylsilane, bisindenylsilane, trisindenylsilane, tetrakisindenylsilane, monoindenylmonomethylsilane, monoindene Nylmonoethylsilane, monoindenyldimethylsilane, monoindenyldiethylsilane, monoindenyltrimethylsilane, monoindenyltriethylsilane, monoindenylmonomethoxysilane, monoindenylmonoethoxysilane, monoindenylmonophenoxysilane, Bisindenylmonomethylsilane, bisindenylmonoethylsilane, bisindenyldimethylsilane, bisindenyldiethylsilane, bisindenylmethylethylsilane, bisindenyldipropylsila , Bisindenylethylpropylsilane, bisindenyldiephenylsilane, bisindenylphenylmethylsilane, bisindenylmonomethoxysilane, bisindenylmonoethoxysilane, trisindenylmonomethylsilane, trisindenylmonoethylsilane, tris Indenyl monomethoxysilane,
Trisindenyl monoethoxysilane, 3-methylindenylsilane, bis-3-methylindenylsilane, 3-
Methylindenylmethylsilane, 1,2-dimethylindenylsilane, 1,3-dimethylindenylsilane,
1,2,4-trimethylindenylsilane, 1,2,
3,4-tetramethylindenylsilane, pentamethylindenylsilane and the like.

Further, any one of the above-mentioned compounds may be an alkylene group (the carbon number of which is usually 2-8, preferably 2
A compound bound via 3) can also be used as the component (C) of the present invention. For example, bisindenylethane, bis (4,5,6,7-tetrahydro-1-indenyl) ethane, 1,3
-Propandinylbisindene, 1,3-Propandinylbis (4,5,6,7-tetrahydro) indene, Propylenebis (1-indene), Isopropyl (1-indenyl) cyclopentadiene, Diphenylmethylene (9-fluorenyl ) Cyclopentadiene, isopropylcyclopentadienyl-1-fluorene and the like are all compounds usable as the component (C) of the present invention.

Various boranes and / or borates are used as component (D). The first example of borane that can be used in the present invention is a compound represented by R ¹² ₃ B. Here, R ¹² is an aryl group such as phenyl and tolyl having 6 to 20, preferably 6 to ¹² carbon atoms, an aralkyl group such as benzyl, a haloaryl group such as fluorophenyl, difluorophenyl, trifluorophenyl and pentafluorophenyl, A haloaralkyl group such as pentafluorobenzyl is shown. The first example of borane is triphenylborane, tri (o-tolyl) borane, tri (p-tolyl) borane, tri (m-tolyl) borane, tri (o-fluorophenyl) borane, tri (p-fluoro). Phenyl) borane, tri (m-fluorophenyl) borane, tri (3,5-difluorophenyl) borane, tri (pentafluorophenyl) borane are included. Among these, tri (o-fluorophenyl) borane, tri (p-fluorophenyl) borane,
Tri (m-fluorophenyl) borane, tri (3,5-difluorophenyl) borane and tri (pentafluorophenyl) borane are preferable as the component (D) of the present invention, and tri (pentafluorophenyl) borane is particularly preferable.

The second example of the borane which can be used as the component (D) is a higher borohydride complex, that is, a polyboron compound having a boron number of 4 or more, usually 4 to 12, produced by thermal decomposition of diborane. This includes tetraborane, decaborane, etc. A third example of borane that can be used as component (D) is a carborane containing carbon in its molecule in the above polyboron compound, which includes 7,8-dicarbaundecaborane, 2,7 -Dicarbaundecaborane, undecahydride-7,8-dimethyl-7,8-dicarbaundecaborane, dodecahydride-11-methyl-2,7-
It includes dicarbaundecaborane, 4-carbanonaborane, 1,3-dicarbanonaborane, 6,9-dicarbadecaborane, dodecahydrido-1-methyl-1,3-dicarbanonaborane and the like.

The borate used as the component (D) in the present invention means an ate complex containing boron. A first example of a borate is a higher borohydride anion complex, a compound derived from diborane and tetrahydroborate, which includes tributylammonium nonaborate, tributylammonium decaborate, tributylammonium undecaborate, tributylammonium. Dodecaborate, dimethylanilinium nonaborate, dimethylanilinium decaborate,
Dimethylanilinium undecaborate, dimethylanilinium dodecaborate, triphenylphosphonium nonaborate, triphenylphosphonium decarbolate,
Triphenylphosphonium undecaborate, triphenylphosphonium dodecaborate, tritylnonaborate, trityldecaborate, tritylundecaborate, trityldodecaborate, ferrocenium nonaborate, ferrocenium decaprate, ferrocenium undecaborate, ferro Included are cenium dodecaborate, tropylium nonaborate, tropylium decaborate, tropylium undecaborate, tropylium dodecaborate, and the like.

The second example of the borate is represented by the general formula: [L ¹ -H] ⁺ [BR ¹³ R ¹⁴ X ² X ³ ] ^- (1). In the formula, L ¹ is a neutral Lewis base, H is a hydrogen atom, and [L ¹ -H] is a Bronsted acid such as ammonium, anilinium, or phosphonium. Ammonium as a Bronsted acid includes trialkyl-substituted ammonium such as trimethylammonium, triethylammonium, tripropylammonium, tributylammonium, tri (n-butyl) ammonium, dialkylammonium such as di (n-propyl) ammonium, dicyclohexylammonium. Is included. Anilinium as Bronsted acid has N,
N, N-dialkylanilinium such as N-dimethylanilinium, N, N-diethylanilinium, and N, N-2,4,6-pentamethylanilinium are included, and phosphonium as a Bronsted acid is trivalent. Examples include triarylphosphonium and trialkylphosphonium such as phenylphosphonium, tributylphosphonium, tri (methylphenyl) phosphonium, and tri (dimethylphenyl) phosphonium. R ¹³ and R ^{14 each} independently represent an aromatic hydrocarbon group having 6 to 20 carbon atoms, preferably 6 to ¹⁶ carbon atoms or a substituted aromatic hydrocarbon group, which may be linked to each other by a bridging group. As the substituent of the substituted aromatic hydrocarbon group, a hydrocarbon group having 1 to 4 carbon atoms (for example, an alkyl group represented by methyl, ethyl, propyl, isopropyl, etc.) and halogen (fluorine, chlorine, bromine, iodine, etc.) ) Is mentioned. X ² and X ³ are hydrogen, halogen, a hydrocarbon group having 1 to 20 carbon atoms (for example, methyl, ethyl, propyl, isopropyl,
Cyclopropyl, butyl, isobutyl, t-butyl, cyclobutyl, pentyl, isopentyl, neopentyl,
Alkyl groups such as cyclopentyl, hexyl, isohexyl, cyclohexyl, heptyl, octyl; vinyl,
Alkenyl group such as allyl; aryl group such as phenyl, tolyl, xylyl, mesityl, indenyl, naphthyl; aralkyl group such as benzyl, trityl, phenethyl, styryl, benzhydryl, phenylbutyl, phenylpropyl, neofil); Derived halogen-substituted hydrocarbon group (substituted halogen is, for example, fluorine, chlorine, bromine, iodine).

Specific examples of the compounds contained in the second example of borate include tributylammonium tetra (p-tolyl) borate, tributylammonium tetra (m-tolyl) borate, tributylammonium tetra (o-fluorophenyl) borate, Tributylammonium tetra (p-fluorophenyl) borate, tributylammonium tetra (m-fluorophenyl) borate, tributylammonium tetra (3,5-difluorophenyl)
Borate, dimethylanilinium tetra (o-tolyl) borate, dimethylanilinium tetra (p-tolyl) borate, dimethylanilinium tetra (m-tolyl) borate, dimethylanilinium tetra (o-fluorophenyl) borate, dimethylanilinium Tetra (p-fluorophenyl) borate, dimethylanilinium tetra (m-fluorophenyl) borate, dimethylanilinium tetra (3,5-difluorophenyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate, triphenylphosphonium tetra Phenylborate, triphenylphosphonium tetra (o-tolyl) borate, triphenylphosphonium tetra (p-tolyl) borate, triphenylphosphonium tetra (m-tolyl)
Borate, triphenylphosphonium tetra (o-fluorophenyl) borate, triphenylphosphonium tetra (p-fluorophenyl) borate, triphenylphosphonium tetra (m-fluorophenyl) borate, triphenylphosphonium tetra (3,5-difluorophenyl) Borate, triphenylphosphonium tetra (pentafluorophenyl) borate, triethylammonium tetra (o-fluorophenyl) borate, triethylammonium tetra (pentafluorophenyl) borate, triethylammonium tetra (phenyl) borate, tripropylammonium tetraphenylborate, tri (N-Butyl) ammonium tetraphenylborate, trimethylammonium tetra (p-tolyl)
Borate, trimethylammonium tetra (o-tolyl) borate, tripropylammonium tetra (o,
Trialkyl-substituted ammonium such as p-dimethylphenyl) borate, tributylammonium tetra (p-trifluoromethylphenyl) borate, tributylammonium tetra (pentafluorophenyl) borate, tri (n-butyl) ammonium tetra (o-tolyl) borate N, such as salt, N, N-dimethylanilinium tetra (phenyl) borate, N, N-diethylanilinium tetra (phenyl) borate, N, N-2,4,6-pentamethylanilinium tetra (phenyl) borate , N-dialkylanilinium salt, di (1-propyl) ammonium tetra (pentafluorophenyl)
Examples thereof include dialkylammonium salts such as borate and dicyclohexylammonium tetraphenylborate. Among these, tributylammonium tetra (o-fluorophenyl) borate, tributylammonium tetra (p-fluorophenyl) borate, tributylammonium tetra (m-fluorophenyl) borate, tributylammonium tetra (3,5-difluorophenyl) borate, tributyl Ammonium tetra (pentafluorophenyl) borate, dimethylanilinium tetra (o-fluorophenyl) borate, dimethylanilinium tetra (p-fluorophenyl) borate, dimethylanilinium tetra (m-fluorophenyl) borate, dimethylanilinium tetra ( 3,5-difluorophenyl) borate and dimethylanilinium tetra (pentafluorophenyl) borate are preferred, and tributylammonium tetra (pentafluoro) Phenyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate is particularly preferred.

The third example of a borate of the general formula: represented by ^{[L 2 -H] [(CX} 4) e (BX 5) f X 6 g] h- (2). In the formula, [L ² -H] represents a hydrogen ion, an ammonium cation, a substituted ammonium cation, a phosphonium group or a substituted phosphonium group. As the substituent in the substituted ammonium cation or the substituted phosphonium group, a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms (for example, methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, isobutyl, t -Alkyl groups such as butyl, cyclobutyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, isohexyl, cyclohexyl, heptyl and octyl; alkenyl groups such as vinyl and allyl; aryl groups such as phenyl, tolyl, xylyl, mesityl, indenyl and naphthyl. Aralkyl groups such as benzyl, trityl, phenethyl, styryl, benzhydryl, phenylbutyl, phenylpropyl, neophyll) and halogen-substituted hydrocarbon groups derived from these hydrocarbon groups (substituted halo) Emissions Example: fluorine, chlorine, bromine, iodine) and the like, and these substituents is substituted with three or less of the hydrogen atoms of the ammonium cation or phosphonium. Specific examples of [L ² -H] include, as substituted ammonium cations, trialkyl-substituted ammonium cations such as trimethylammonium, triethylammonium, tripropylammonium, tributylammonium, tri (n-butyl) ammonium, and di ( n
There are dialkylammonium cations such as -propyl) ammonium, dicyclohexylammonium. Substituted phosphonium groups include triarylphosphoniums such as triphenylphosphonium, tributylphosphonium, tri (methylphenyl) phosphonium, tri (dimethylphenyl) phosphonium and trialkylphosphoniums. X ⁴ , X ⁵ and X
⁶ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms (for example, methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, isobutyl, t-butyl, cyclobutyl, pentyl, Alkyl groups such as isopentyl, neopentyl, cyclopentyl, hexyl, isohexyl, cyclohexyl, heptyl and octyl; alkenyl groups such as vinyl and allyl; aryl groups such as phenyl, tolyl, xylyl, mesityl, indenyl and naphthyl; benzyl, trityl, phenethyl, Aralkyl groups such as styryl, benzhydryl, phenylbutyl, phenylpropyl, and neophyll), halogen-substituted hydrocarbon groups derived from the above hydrocarbon groups (substituted halogen is, for example, fluorine, chlorine, bromine, iodine) or organic moieties are Prime to 20, preferably 1 to 12
In the hydrocarbon substituent of, the metal is an organic metalloid group selected from Group IV-A of the periodic table. e and g are integers of 0 or more, and h is an integer of 1 or more. e + g + h is usually an even integer from 2 to 8 and f is usually an integer from 5 to 22.

Specific examples of the compounds included in the third example of borate include tributylammonium-1-carbaundecaborate, tributylammonium-1-carbadecaborate, tributylammonium-6-carbaundecaborate, Tributylammonium-7-carbaundecaborate, tributylammonium-7,8-dicarbaundecaborate, tributylammonium-2,9-dicarbaundecaborate, methylammonium 1-carbadodecaborate, ethylammonium 1-carbadodecaborate, Propyl ammonium 1-carbadodecaborate, isopropyl ammonium 1-carbadodecaborate, (n-butyl) ammonium 1-carbadodecaborate, anilinium 1-carbadodecaborate, (p
-Tolyl) ammonium 1-carbadodecaborate and other monohydrocarbyl-substituted ammonium salts, dimethylanilinium-1-carbaundecaborate, dimethylanilinium-1-carbadodecaborate, dimethylanilinium-1-carbadecaborate, dimethylanili Nium-6-
Carbaundecaborate, dimethylanilinium-7-carbaundecaborate, dimethylanilinium-7,8-dicarbaundecaborate, dimethylanilinium 2,9-dicarbaundecaborate, dimethylammonium 1-carbadodecaborate, diethyl Ammonium 1-carbadodecaborate, dipropylammonium 1-carbadodecaborate, diisopropylammonium 1-carbadodecaborate, di (n-butyl) ammonium 1-carbadodecaborate, diphenylammonium 1-carbadodecaborate, di (p-tolyl) ) Ammonium 1-
Dihydrocarbyl-substituted ammonium salt such as carbadodecaborate, trimethylammonium 1-carbadodecaborate, triethylammonium 1-carbadodecaborate, tripropylammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-carbadodecaborate, tri Phenylammonium 1-carbadodecaborate, tri (p-tolyl) ammonium 1-carbadodecaborate, N, N-dimethylanilinium 1
Examples include trihydrocarbyl-substituted ammonium salts such as -carbadodecaborate and N, N-diethylanilinium 1-carbadodecaborate.

A fourth example of the borate is represented by the general formula: [L ² -H] [[<(CX ⁴ ) _i (BX ⁵ ) _j (X ⁶ ) _k ＞ ^l- ] ₂ M ^{n +} ] ^m- (3) It is represented by. In the formula, [L ² -H], X ⁴ , X ⁵ and X ⁶
Indicates the same content as defined by the general formula (2), and M
Indicates a transition metal such as Cr, Mn, Fe, Co or Ni.
i and k are the same or different integers of 0 or more. l is an integer of 2 or more, and i + k + l is usually an even integer of 4 to 8. j is usually an integer from 6 to 12. n
Is an integer such that 2 l −n = m, and m is an integer of 1 or more.

Specific examples of the compounds included in the fourth example of borate include tributylammonium bis (nonahydride-1,3-dicarbaunaborate) cobaltate (I
II), tributylammonium bis (undecahydride
-7,8-Dicarbaundecaborate) Ferrate (III),
Tributylammonium bis (undecahydride-7,8-
Dicarbaundecaborate) cobaltate (III), tributylammonium bis (undecahydrido-7,8-dicarbaundecaborate) nickelate (III), tributylammonium bis (dodecahydridodicarbadodecaborate) cobaltate (III), tributyl Ammonium bis (undecahydride-7-carbaundecaborate) chromate (III), tributylammonium bis (undecahydrido-7-carbaundecaborate) manganate (IV), tributylammonium bis (undecahydrido-7-) Carbaundecaborate) Cobaltate (III), Tributylammonium bis (Undecahydrido-7-carbaundecaborate) Nickelate (I
V), dimethylanilinium bis (nonahydrido-1,3-dicarbaunaborate) cobaltate (III), dimethylanilinium bis (undecahydrido-7,8-dicarbaundecaborate) ferrate (III), dimethylanilinium Bis (undecahydride-7,8-dicarbaundecaborate) cobaltate (III), dimethylanilinium bis (undecahydrido-7,8-dicarbaundecaborate) nickelate (III), dimethylanilinium bis (dodeca) Hydride dicarbadodecaborate) cobaltate (III), dimethylanilinium bis (undecahydrido-7-carbaundecaborate) chromate (II
I), dimethylanilinium bis (undecahydride-7-
Carbaundecaborate) Manganate (IV), Dimethylanilinium Bis (Undecahydrido-7-carbaundecaborate) Cobaltate (III), Dimethylanilinium Bis (Undecahydrido-7-carbaundecaborate) Nickelate (IV), triphenylphosphonium bis (nonahydrido-1,3-dicarbaunaborate) cobaltate (III), triphenylphosphonium bis (undecahydrido-7,8-dicarbaundecaborate) ferrate (III), triphenyl Phosphonium bis (undecahydride-7,8-dicarbaundecaborate) cobaltate (III), triphenylphosphonium bis (undecahydrido-7,8-dicarbaundecaborate) nickelate (III), triphenylphosphonium bis ( Dodeca hydrido dicarbadodecaborate) cobalte Doo (II
I), triphenylphosphonium bis (undecahydrido-7-carbaundecaborate) chromate (III), triphenylphosphonium bis (undecahydrido-7-carbaundecaborate) manganate (IV), triphenylphosphonium bis (Undecahydride-7-carbaundecaborate) cobaltate (III) and triphenylphosphonium bis (undecahydrido-7-carbaundecaborate) nickelate (IV).

A fifth example of the borate is represented by the general formula: [L ³ ] ⁺ [BR ¹³ R ¹⁴ X ² X ³ ] ^- (4). In the formula, L ³ represents a carbocation,
R ¹³ , R ¹⁴ , X ² and X ³ have the same meaning as defined in the general formula (1). The carbocation referred to herein includes, for example, methyl cation, ethyl cation, propyl cation, isopropyl cation, butyl cation,
It includes so-called alkyl cations such as isobutyl cation, t-butyl cation, pentyl cation and neopentyl cation, cycloalkyl cations such as tropylium cation, benzyl cation, trityl cation and the like.

Specific examples of the compounds included in the fifth example of borate include trityl tetraphenyl borate,
Trityl tetra (o-tolyl) borate, trityl tetra (p-tolyl) borate, trityl tetra (m-tolyl) borate, trityl tetra (o-fluorophenyl) borate, trityl tetra (p-fluorophenyl) borate,
Trityl tetra (m-fluorophenyl) borate, trityl tetra (3,5-difluorophenyl) borate, trityl tetra (pentafluorophenyl) borate, tropylium tetraphenyl borate, tropylium tetra (o-tolyl) borate, tropylium tetra (P-tolyl) borate, tropylium tetra (m-tolyl) borate, tropylium tetra (o-fluorophenyl) borate, tropylium tetra (p-fluorophenyl) borate, tropylium tetra (m-fluorophenyl) borate, Examples thereof include tropylium tetra (3,5-difluorophenyl) borate and tropylium tetra (pentafluorophenyl) borate. Among these, trityl tetra (o-fluorophenyl) borate, trityl tetra (p-fluorophenyl) borate, trityl tetra (m-fluorophenyl) borate, trityl tetra (3,5-difluorophenyl) borate, trityl tetra (pentafluoro) Phenyl) borate, tropylium tetra (o-fluorophenyl) borate, tropylium tetra (p-fluorophenyl) borate, tropylium tetra (m-fluorophenyl) borate, tropylium tetra (3,5-difluorophenyl) borate, Tropylium tetra (pentafluorophenyl) borate is preferable, and trityl tetra (pentafluorophenyl) borate and tropylium tetra (pentafluorophenyl) borate are particularly preferable.

The sixth example of the borate is represented by the general formula: [R ¹⁵ ₂ M] ⁺ [BR ¹³ R ¹⁴ X ² X ³ ] ^- (5). In the formula, R ¹⁵ represents a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group or a substituted indenyl group, and M represents Cr, Mn, Fe, Co, Ni.
And other transition metals. And R ¹³ , R ¹⁴ , X ² and X
³ has the same content as defined by the general formula (1).
In the above substituted cyclopentadienyl group or substituted indenyl group, the substituent is a halogen atom,
A hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms is included.

Specific examples of the compounds included in the sixth example of borate include ferrocenium tetraphenyl borate, ferrocenium tetra (o-tolyl) borate, ferrocenium tetra (p-tolyl) borate, Ferrocenium tetra (m-tolyl) borate, Ferrocenium tetra (o-fluorophenyl) borate, Ferrocenium tetra (p-fluorophenyl) borate, Ferrocenium tetra (m-fluorophenyl) borate, Ferrocenium Examples thereof include tetra (3,5-difluorophenyl) borate and ferrocenium tetra (pentafluorophenyl) borate. Among them, ferrocenium tetra (o-fluorophenyl) borate, ferrocenium tetra (p-fluorophenyl) borate, ferrocenium tetra (m-fluorophenyl) borate, ferrocenium tetra (3,5-difluorophenyl) Borate and ferrocenium tetra (pentafluorophenyl) borate are preferable, and ferrocenium tetra (pentafluorophenyl) borate is particularly preferable.

The seventh example of the borate is represented by the general formula: [L ³ ] ⁺ [(CX ⁴ ) _e (BX ⁵ ) _f X ⁶ _g ] ^h- (6). In the formula, L ³ has the same contents as defined by the general formula (4). Also X ⁴ , X ⁵ , X ⁶ , e, f, g
And h have the same meaning as defined in the general formula (2). Specific examples of the compounds included in the seventh example of borate are: trityl-1-carbaundecaborate, trityl-1-carbadodecaborate, trityl-1-carbadecaborate, trityl-6-carbaundecarate. Borate, trityl-7-carbaundecaborate, trityl-7,8-dicarbaundecaborate, trityl-2,9-dicarbaundecaborate, tropylium-1-carbaundecaborate,
Tropylium-1-carbadodecaborate, tropylium-
Examples include 1-carbadecaborate, tropylium-6-carbaundecaborate, tropylium-7-carbaundecaborate, tropylium-7,8-dicarbaundecaborate, tropylium-2,9-dicarbaundecaborate. it can.

An eighth example of the borate is represented by the general formula: [R ¹⁵ ₂ M] ⁺ [(CX ⁴ ) _e (BX ⁵ ) _f X ⁶ _g ] ^h- (7). In the formula, R ¹⁵ and M have the same contents as defined in the general formula (5), and X ⁴ , X ⁵ , X ⁶ , e,
f, g and h have the same contents as defined in the general formula (2). Specific examples of the compounds included in the eighth example of borate are ferrocenium-1-carbaundecaborate, ferrocenium-1-carbadodecaborate, ferrocenium-1-carbadecaborate, and ferrocenium-6-.
Carbaundecaborate, ferrocenium-7-carbaundecaborate, ferrocenium-7,8-dicarbaundecaborate, ferrocenium-2,9-dicarbaundecaborate and the like can be exemplified.

The ninth example of the borate is represented by the general formula: [L ³ ] ⁺ [[<(CX ⁴ ) _i (BX ⁵ ) _j (X ⁶ ) _k ＞ ^l- ] ₂ M ^{n +} ] ^m- (8) expressed. In the formula, L ³ has the same meaning as defined in the general formula (4), and X ⁴ , X ⁵ , X ⁶ , M, i, j, k
, L, n and m have the same meaning as defined in the general formula (3). Specific examples of the compounds included in the ninth example of borate are tritylbis (nonahydrido-1,3-
Dicarbaunaborate) Cobaltate (III), Tritylbis (undecalide-7,8-dicarbaundecaborate) Ferrate (III), Tritylbis (undecahydrido-7,8-dicarbaundecaborate) cobaltate (I)
II), tritylbis (undecahydrido-7,8-dicarbaundecaborate) nickelate (III), tritylbis (dodecahydridodicarbadodecaborate) cobaltate (III), tritylbis (undecahydrido-7-carbaundecaborate) ) Chromate (III), Tritylbis (Undecahydrido-7-carbaundecaborate) Manganate (IV), Tritylbis (Undecahydrido-7)
-Carbaundecaborate) cobaltate (III), tritylbis (undecahydrido-7-carbaundecaborate) nickelate (IV), tropyliumbis (nonahydrido-1,3-dicarbaunaborate) cobaltate (II)
I), tropylium bis (undecahydrido-7,8-dicarbaundecaborate) ferrate (III), tropylium bis (undecahydrido-7,8-dicarbaundecaborate) cobaltate (III), tropylium bis (Undecahydrido-7,8-dicarbaundecaborate) Nickelate (III), tropylium bis (dodecahydrido dicarbadodecaborate) cobaltate (III), tropylium bis (undecahydrido-7-carbaundecaborate) ) Chromate (III), tropylium bis (undecahydrido-7-carbaundecaborate) manganate (IV), tropylium bis (undecahydrido-7-carbaundecaborate) cobaltate (III), tropylium bis (Undecahydride-7-carbaundecaborate) Nickelate (IV), etc. .

A third example of borate is the general formula: [R ¹⁵ ₂ M] ⁺ [[<(CX ⁴ ) _i (BX ⁵ ) _j (X ⁶ ) _k ＞ ^1- ] ₂ M ^{n +} ] ^m- (9 ). In the formula, R ¹⁵ and M have the same contents as defined in the general formula (5), and X ⁴ , X ⁵ , X ⁶ , M,
i, j, k, l, n and m have the same meaning as defined in the general formula (3). Specific examples of the compounds included in the first example of borate include ferrocenium bis (nonahydrido-1,3-dicarbaunaborate) cobaltate (I
II), Ferrocenium bis (undecahydride-7,8-dicarbaundecaborate) ferrate (III), Ferrocenium bis (undecahydrido-7,8-dicarbaundecaborate) cobaltate (III), Ferro Cenium bis (undecahydrido-7,8-dicarbaundecaborate) nickelate (III), ferrocenium bis (dodecahydridodicarbadodecaborate) cobaltate (II
I), ferrocenium bis (undecahydrido-7-carbaundecaborate) chromate (III), ferrocenium bis (undecahydrido-7-carbaundecaborate) manganate (IV), ferrocenium bis Examples include (undecahydride-7-carbaundecaborate) cobaltate (III), ferrocenium bis (undecahydrido-7-carbaundecaborate) nickelate (IV), and the like.

The first olefin polymerization catalyst according to the present invention is composed of the above-mentioned components (A) to (D), but the second olefin polymerization catalyst proposed by the present invention has the above-mentioned 4
It is composed of 5 components obtained by adding a modified organoaluminum compound as the component (E) to the components. The component (E) of the present invention is usually 1 to 100, preferably 1 to 50 in the molecule.
A linear or cyclic modified organoaluminum compound having a number of Al-O-Al bonds is used. Such a modified organoaluminum compound can be usually obtained by reacting an organoaluminum compound with water, and the reaction is generally carried out in an inert hydrocarbon. As the inert hydrocarbon, any of aliphatic hydrocarbons such as pentane, hexane, cyclohexane, methylcyclohexane, benzene, toluene and xylene, alicyclic hydrocarbons or aromatic hydrocarbons can be used, but aliphatic hydrocarbons can be used. Preference is given to using hydrocarbons or aromatic hydrocarbons.

The organoaluminum compound used to prepare the modified organoaluminum compound has the general formula: R ¹⁶ _y AlX ⁷
_3-y (wherein R ¹⁶ has 1 to 18 carbon atoms, preferably 1 to 1 carbon atoms)
2 represents a hydrocarbon group such as an alkyl group, an alkenyl group, an aryl group and an aralkyl group, and X ⁷ represents a hydrogen atom or a halogen atom. y is an integer of 1≤y≤3), but any of trialkylaluminum is preferably used. The alkyl group of trialkylaluminum is methyl, ethyl, propyl,
It may be any of isopropyl, butyl, isobutyl, pentyl, hexyl, octyl, decyl and dodecyl, but methyl is particularly preferable.

The reaction ratio of water and the organoaluminum compound (water / Al molar ratio) is preferably 0.25 / 1 to 1.2 / 1, and particularly preferably 0.5 / 1 to 1/1. The reaction temperature is generally −70 to 100 ° C., preferably −20 to 20.
It is in the range of ° C. The reaction time is usually selected in the range of 5 minutes to 24 hours, preferably 10 minutes to 5 hours. As the water required for the reaction, so-called water can be used, and also water of crystallization contained in copper sulfate hydrate, aluminum sulfate hydrate, etc. can be used. Water required for the reaction can also be supplied. Incidentally, among the modified organoaluminum compounds produced by the reaction of water and the organoaluminum compound, those obtained by the reaction of alkylaluminum and water are usually called aluminoxane, and as the component (E) of the present invention, Methylaluminoxane is particularly preferred.

The first olefin polymerization catalyst according to the present invention comprises the above four components (A) to (D), and the second olefin polymerization catalyst comprises the five components (A) to (E). These catalysts can be obtained by bringing them into contact with each other.
It is also possible to carry out polymerization by supporting it on an inorganic carrier such as silica or silica-alumina and / or a granular polymer carrier.

The catalyst of the present invention can be prepared by contacting each constituent by the following procedure. 1. A method of adding (B) to (A), further adding (C), and further adding (D). 2. A method of adding (B) to (A), further adding (D), and further (C). 3. A method of adding (C) to (A), further adding (B), and further adding (D). 4. A method of adding (C) to (A), further adding (D), and further adding (B). 5. A method of adding (D) to (A), further adding (B), and further (C). 6. A method of adding (D) to (A), further adding (C), and further adding (B). 7. A method of adding (A) to (B), further adding (C), and further (D). 8. A method of adding (A) to (B), further adding (D), and further (C). 9. A method of adding (C) to (B), further adding (A), and further (D). 10. (C) is added to (B), and then (D) and
A method of adding (A). 11. A method of adding (D) to (B), further adding (A), and further (C). 12. A method of adding (D) to (B), further adding (C), and further adding (A). 13. A method of adding (A) to (C), further adding (B), and further adding (D). 14. A method of adding (A) to (C), further adding (D) and further (B). 15. A method of adding (B) to (C), further adding (A), and further (D). 16. A method of adding (B) to (C), further adding (D), and further adding (A). 17． A method of adding (D) to (C), further adding (A), and further (B). 18. A method of adding (D) to (C), further adding (B), and further adding (A). 19. A method of adding (A) to (D), further adding (B), and further adding (C). 20. A method of adding (A) to (D), further adding (C), and further adding (B). 21. A method of adding (B) to (D), further adding (A), and further (C). 22. A method of adding (B) to (D), further adding (C), and further adding (A). 23. A method of adding (C) to (D), further adding (A), and further (B). 24. A method of adding (C) to (D), further adding (B), and further adding (A). Further, as a method of dividing the constituent components into contact with each other, for example, 25. (B) is added to (D), and (A), (B),
A method of adding (C). 26. (D) is added to (B), and (A), (B),
A method of adding (C). Is also effective. Further, it is also possible to bring the components, which have been brought into contact with each other in advance, into contact with each other. For example, 27. A method of adding the contact substances (A), (B), and (C) (this contact order is arbitrary) to (D). 28. (B) is added to (D), and (A), (B),
A method of adding the contact product of (C) (this contact order is arbitrary). 29. A method of adding (B) to (D) and further adding the contact substances (A) and (C) (the contact order is arbitrary). 30. (D) is added to (B), and (A), (B),
A method of adding the contact product of (C) (this contact order is arbitrary). Can also be adopted.

As the contacting method when the component (E) is used in combination, a method of adding the component (E) at any contacting step in the contacting methods 1 to 30 can be adopted.
For example, 31. (D) is added to (E), and (A), (B), (C)
The method of adding the contact object (the contact order is arbitrary). 32. (E) is added to (D), and (A), (B), (C)
The method of adding the contact object (the contact order is arbitrary). 33. A method in which (D) is added to (E), then (B) is added, and then the contact substances (A), (B), and (C) (this contact order is arbitrary) are added. 34. A method in which (B) is added to (E), then (D) is added, and then the contact substances (A), (B), and (C) (this contact order is arbitrary) are added. 35. A method in which (B) is added to (D), then (E) is added, and then the contact substances (A), (B), and (C) (the contact order is arbitrary) are added. 36. A method in which (E) is added to (D), then (B) is added, and then the contact substances (A), (B), and (C) (this contact order is arbitrary) are added. 37. A method in which (E) is added to (B), then (D) is added, and then the contact substances (A), (B), and (C) (this contact order is arbitrary) are added. 38. A method in which (D) is added to (B), then (E) is added, and then the contact substances (A), (B), and (C) (this contact order is arbitrary) are added. Can be adopted. Among the contacting procedures listed above, the methods 10, 11, 18, 22-38 are preferred. The mutual contact of each component can be carried out without a solvent, but generally, in the presence of an inert hydrocarbon solvent such as benzene, hexane, toluene, xylene, etc., usually -100 to 200 ° C, preferably Is -50 to 100 ° C
In the temperature range of 10 minutes to 50 hours, preferably 30 minutes to
It is possible to contact each component for 24 hours.

The proportion of each component used is 0.0 mol for each of component (B) and component (C) per mol of component (A).
1 to 1000 mol, preferably 0.1 to 100 mol,
More preferably, it is in the range of 0.5 to 50 mol. The ratio of the component (D) used is the atomic ratio of boron of the component (D) to the transition metal of the component (A), boron / transition metal = 0.
It is in the range of 1 to 1000, preferably 0.2 to 100. When the component (E) is used in combination, the atomic ratio of aluminum of the component (E) to the transition metal of the component (A), aluminum / transition metal is 0.1 to 1000, preferably 1 to 1.
It is adjusted to 100, more preferably 1 to 80. The ratio of the component (D) and the component (E) when the component (E) is used in combination is not particularly limited, but is the atomic ratio of aluminum of the component (E) to boron of the component (D),
Usually, the range of aluminum / boron is 0.01 to 10,000, preferably 0.1 to 1,000. When a carrier is used, based on the amount of the transition metal of the component (A) contained in the catalyst of the present invention with respect to 1 g of the carrier,
It is preferably in the range of 0.0001 g to 1 g. When the catalyst of the present invention is prepared by bringing the respective components into contact with each other in an inert hydrocarbon solvent, the prepared catalyst can be directly used in the polymerization reaction without being separated from the inert hydrocarbon solvent. If the solvent can be separated by an appropriate means such as precipitation or drying, the prepared catalyst can be once taken out from the solvent and used as a solid catalyst for polymerization. Furthermore, even in the process of preparing the catalyst, it is possible to proceed to the next contact stage without separating the inert hydrocarbon solvent for each contact stage of each component, or if the solvent is separated, then proceed to the next contact stage. You can also

In the catalyst of the present invention, the components (A) to
The preferred combination of (D) is as follows.
When the component (E) is used in combination, the component (E) is added to each of these combinations. Combination Example 1 Component (A): Tetraalkoxyzirconium compound such as tetrapropoxyzirconium and tetrabutoxyzirconium, Component (B): Alkylaluminum hydride compound such as diethylaluminum hydride, diisobutylaluminum hydride, Component (C): Indene, methylindene Indene derivatives such as or cyclopentadiene derivatives such as cyclopentadiene, methylcyclopentadiene, dimethylcyclopentadiene, Component (D): triarylboron compounds such as tri (pentafluorophenyl) borane. Combination Example 2 Component (A): Tetraalkoxyzirconium compound such as tetrapropoxyzirconium and tetrabutoxyzirconium, Component (B): Alkylaluminum hydride compound such as diethylaluminum hydride, diisobutylaluminum hydride, Component (C): Indene, methylindene Indene derivatives such as or cyclopentadiene, methylcyclopentadiene, cyclopentadiene derivatives such as dimethylcyclopentadiene, Component (D): tributylammonium tetra (pentafluorophenyl) borate, N, N-dimethylanilinium tetra (pentafluorophenyl) borate , N,
A boron-containing ate complex of N-diethylanilinium tetra (pentafluorophenyl) borate, trityl tetra (pentafluorophenyl) borate, tropylium tetra (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate. Combination Example 3 Component (A): tetraalkoxyzirconium compound such as tetrapropoxyzirconium and tetrabutoxyzirconium, component (B): alkylaluminum hydride compound such as diethylaluminum hydride and diisobutylaluminum hydride, component (C): bisindenyl A compound in which an indene derivative such as ethane or cyclopentadienylfluorenylisopropane, a cyclopentadiene derivative, a fluorene derivative is bonded through an alkylene group, or a compound represented by the general formula (C) such as dimethylsilylbiscyclopentadiene
p) a compound represented by _L SiR ¹¹ _4-L , component (D): a triarylboron compound of tri (pentafluorophenyl) borane. Combination Example 4 Component (A): Tetraalkoxyzirconium compound such as tetrapropoxyzirconium and tetrabutoxyzirconium, Component (B): Alkylaluminum hydride compound such as diethylaluminum hydride and diisobutylaluminum hydride, Component (C): Bisindenylethane Alternatively, a compound in which an indene derivative such as cyclopentadienylfluorenylisopropane, a cyclopentadiene derivative, a fluorene derivative is bonded through an alkylene group, or a compound represented by the above general formula (C) such as dimethylsilylbiscyclopentadiene
p) a compound represented by _L SiR ¹¹ _4-L , component (D): tributylammonium tetra (pentafluorophenyl) borate, N, N-dimethylanilinium tetra (pentafluorophenyl) borate, N,
A boron-containing ate complex of N-diethylanilinium tetra (pentafluorophenyl) borate, trityl tetra (pentafluorophenyl) borate, tropylium tetra (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate.

When olefins are homopolymerized or copolymerized using the catalyst of the present invention, the components (A) to
It is customary to prepare a catalyst composed of (D) or components (A) to (E) in advance and supply this to the polymerization system. However, only the components (A) to (C) are previously contacted,
A method of activating the catalyst of the present invention by bringing the component (D) into contact with the contact product in the polymerization system, or from the components (A) to
It is also possible to employ a method in which (D) is contacted in advance and the contact product is contacted with component (E) in the polymerization system to further improve the activity of the catalyst of the present invention. Furthermore, in homopolymerization or copolymerization of olefins using the catalyst of the present invention, the component (D) or the component (E) can be additionally introduced during the progress of the polymerization reaction.

When the component (E) is added in the polymerization system, the amount of addition is such that the atomic ratio of aluminum to transition metal of the catalyst in the reaction system, aluminum / transition metal is 0.1 to 10.
00, preferably in the range of 1-100.

The starting olefins that can be homopolymerized or copolymerized in the presence of the catalyst of the present invention include α-olefins, cyclic olefins, dienes, trienes and styrene analogs. The α-olefins include those having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms. Specifically, ethylene, propylene, butene-1, hexene-
Examples include 1,4-methylpentene-1 and the like. The α-olefins can be homopolymerized by using the catalyst of the present invention and can also be copolymerized, and the copolymerization includes alternating copolymerization, random copolymerization, and block copolymerization. . For the copolymerization of α-olefins, ethylene and propylene, ethylene and butene-1, ethylene and hexene-1, ethylene and 4-methylpentene-1, such as ethylene and carbon number 3 to 12, preferably 3 to. 8 α-
When copolymerizing with an olefin, propylene and butene-
1, propylene and 4-methylpentene-1, propylene and 4-methylbutene-1, propylene and hexene-1,
A case in which propylene is copolymerized with an α-olefin having 3 to 12 carbon atoms, preferably 3 to 8 carbon atoms, such as propylene and octene-1, is included. When ethylene or propylene is copolymerized with other α-olefin, the amount of the other α-olefin can be arbitrarily selected within the range of 90 mol% or less of the total monomers, but in general, ethylene is used. In the case of the copolymer, 40 mol% or less, preferably 30 mol% or less,
It is more preferably 20 mol% or less, and in the case of a propylene copolymer, it is selected in the range of 1 to 90 mol%, preferably 5 to 90 mol%, and more preferably 10 to 70 mol%.
The cyclic olefin has 3 to 24 carbon atoms, preferably 3 carbon atoms.
~ 18 can be used in the present invention and include, for example, cyclopentene, cyclobutene, cyclopentene,
Cyclohexene, 3-methylcyclohexene, cyclooctene, cyclodecene, cyclododecene, tetracyclodecene, octacyclodecene, dicyclopentadiene,
Norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-isobutyl-2-norbornene, 5,6-dimethyl-2-norbornene, 5,
5,6-trimethyl-2-norbornene, ethylidene norbornene and the like are included. The cyclic olefin is usually copolymerized with the α-olefin described above, in which case the amount of the cyclic olefin is 50 mol% or less of the copolymer, usually 1 to 50 mol%, preferably 2 to 50 mol. It is in the range of%. The catalyst-polymerizable dienes and trienes of the present invention are polyenes having 4 to 26 carbon atoms, preferably 6 to 26 carbon atoms. Specifically, butadiene, 1,3-pentadiene, 1,4-pentadiene, 1,3-hexadiene,
1,4-hexadiene, 1,5-hexadiene, 1,3
-Cyclohexadiene, 1,4-cyclohexadiene,
1,9-decadiene, 1,13-tetradecadiene, 2,
6-dimethyl-1,5-heptadiene, 2-methyl-
2,7-octadiene, 2,7-dimethyl-2,6-octadiene, 2,3-dimethylbutadiene, ethylidene norbornene, dicyclopentadiene, isoprene,
Examples include 1,3,7-octatriene and 1,5,9-decatriene. When the chain diene or triene is used, it is usually copolymerized with the above-mentioned α-olefin, but the chain diene and / or the chain diene in the copolymer is usually used.
Alternatively, the triene content is generally in the range of 0.1 to 50 mol%, preferably 0.2 to 10 mol%. Styrene analogs that can be used as the raw material olefin are styrene and styrene derivatives, and as the derivatives, t-butylstyrene, α-methylstyrene, p-methylstyrene,
Divinylbenzene, 1,1-diphenylethylene, N,
Examples thereof include N-dimethyl-p-aminoethylstyrene, N, N-diethyl-p-aminoethylstyrene and the like.

The catalyst of the present invention can be suitably used also when a homopolymer or copolymer of olefins is further polymerized with a polar monomer to modify the homopolymer or copolymer. As the polar monomer, methyl acrylate,
Examples of the unsaturated carboxylic acid ester include methyl methacrylate, butyl methacrylate, dimethyl maleate, diethyl maleate, monomethyl maleate, diethyl fumarate, and dimethyl itaconate. The polar monomer content of the modified copolymer is usually
It is in the range of 0.1 to 10 mol%, preferably 0.2 to 2 mol%.

The polymerization reaction can be carried out by slurry polymerization, solution polymerization or gas phase polymerization in the presence of the above-mentioned catalyst of the present invention. In particular, slurry polymerization or gas phase polymerization in which a solvent does not substantially coexist is preferable. The polymerization reaction is substantially carried out in a state where oxygen, water, etc. are cut off, and when a reaction solvent is used, hexane, aliphatic hydrocarbons such as heptane, benzene, toluene, aromatic hydrocarbons such as xylene, cyclohexane, An inert hydrocarbon solvent selected from alicyclic hydrocarbons such as methylcyclohexane is used. The polymerization conditions are a temperature of 20 to 200 ° C., preferably 50 to 100 ° C., a pressure and atmospheric pressure to 70 kg / cm ² G, preferably an atmospheric pressure to 20 kg / cm ² G, and a polymerization time of 5 minutes to 10 ° C. It is usual to employ a time, preferably 5 minutes to 5 hours. The molecular weight of the produced polymer can be adjusted to some extent by changing the polymerization conditions such as the polymerization temperature and the molar ratio of the catalyst, but it is possible to more effectively control the molecular weight by adding hydrogen to the polymerization reaction system. it can.

For the purpose of removing water from the polymerization reaction system, the polymerization reaction can be carried out without trouble even if so-called scavenging is added to the system. For such scavenging,
Organoaluminum compounds represented by trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, triisobutylaluminum, the above-mentioned modified organoaluminum compounds, modified organoaluminum compounds having a branched alkyl group, butyllithium, etc. And organic magnesium such as diethyl magnesium, dibutyl magnesium, butyl magnesium chloride and the like. The catalyst of the present invention can also be used in a multi-stage polymerization mode in which two or more reaction stages having different polymerization conditions such as hydrogen concentration, monomer concentration, polymerization pressure and polymerization temperature are used. Before the main polymerization, the olefins are brought into contact with the catalyst in advance to prepare a catalyst containing a very small amount of polymer,
It is also possible to employ a preliminary polymerization method in which this is subjected to main polymerization.

[0051]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but prior to that, preparation of modified organoaluminum compounds used in the Examples and Comparative Examples will be described. Modified organoaluminum compound (methylaluminoxane)
Preparation of 13 g of copper sulfate pentahydrate was placed in a three-necked flask with a capacity of 300 ml equipped with an electromagnetic induction stirrer and suspended with 50 ml of toluene. Then 150m of a solution of trimethylaluminum with a concentration of 1mmol / ml
l was added dropwise to the above suspension under the temperature condition of 0 ° C. over 2 hours, the temperature was raised to 25 ° C. after completion of the dropping, and the reaction was carried out at that temperature for 24 hours. Then, the reaction product was filtered and toluene in the liquid containing the reaction product was removed to obtain 4 g of white crystalline methylalumoxane (MAO). The physical properties of the polymers obtained in Examples and Comparative Examples were evaluated by the following methods. Melt Index (MI) Measured according to ASTM D 1238-57T. The density was measured according to ASTM D 1505-68. Melting point measurement by differential scanning calorimeter (DSC) Using a DSC-20 type melting point measuring device manufactured by Seiko Denshi KK, a 5 mg sample was held at 180 ° C. for 3 minutes, and then,
The melting point was measured by cooling to 0 ° C. at 10 ° C./minute, holding at 0 ° C. for 10 minutes, and then raising the temperature at 10 ° C./minute. Measurement of molecular weight distribution (Mw / Mn) It was measured at 135 ° C. using Ortho-dichlorobenzene as a solvent, using Gel Permeation Chromatography (Model 150-type) manufactured by Waters.

Example 1 (1) Preparation of transition metal catalyst component Under nitrogen, 150 ml of purified toluene was added to a 300 ml three-necked flask equipped with an electromagnetic induction stirrer, and then 3.3 g of zirconium tetrachloride.
And indene (2.3 g) were added and the mixture was stirred at room temperature for 30 minutes, then the system was kept at 0 ° C. and 2.3 g of catechol borane was added dropwise. After completion of the addition, the system was brought to room temperature and stirred for 24 hours to prepare a transition metal catalyst component. . The concentration of this solution is 0.062 mmol / ml as Zr. (2) Contact of transition metal catalyst component with promoter 3 ml of the above solution was sampled in a 50 ml flask, 3.7 ml of a toluene solution of methylaluminoxane (concentration 1 mmol / ml) was added, and the mixture was stirred at room temperature for 30 minutes. Then 0.2 mmol of triethylammonium tetra (pentafluorophenyl) borate
Was added and stirred at room temperature for 3 hours. (3) Polymerization A 3 L stainless steel autoclave equipped with a stirrer was purged with nitrogen, 1 liter of purified toluene was added, 2 mg of the catalyst obtained in (2) above was added as Zr, and the system was heated to 60 ° C. Is heated to a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio 0.25) at 9 Kgf / cm.
Polymerization was started by injecting so as to be ² G, and a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio of 0.
Polymerization was carried out for 2 hours while continuously supplying 05) while maintaining the total pressure at 9 Kgf / cm ² G. After the polymerization was completed, the excess gas was discharged, the contents were cooled and the contents were taken out.
I got The catalyst efficiency was 10 Kg / gZr. The polymer obtained has a density of 0.9230 g / cm ³ , a melting point of 117.5 ° C., and an MI of 1.
It was 1g / 10min. Example 2 (1) Preparation of transition metal catalyst component 150 ml of purified toluene was added to a 300 ml three-necked flask equipped with an electromagnetic induction stirrer under nitrogen, 3.3 g of tetrapropoxyzirconium and 4.6 g of indene were added, and the mixture was stirred at room temperature for 30 minutes, and then at 0 ° C. While maintaining the system, 3.2 g of diisobutylaluminum hydride was added dropwise, and after completion of the addition, the system was allowed to come to room temperature.
After stirring for a period of time, a transition metal catalyst component was prepared. The concentration of this solution is 0.062 mmol / ml as Zr. (2) Contact of transition metal catalyst component with promoter 3 ml of the above solution was collected in a 50 ml flask and dimethylanilinium tetra (pentafluorophenyl) borate 0.4 m
mol was added and the mixture was stirred at room temperature for 3 hours. (3) Polymerization The addition amount of the catalyst obtained in (2) above to the autoclave is Z
Polymerization was carried out in the same manner as in Example 1 except that r was 1.5 mg. After the completion of the polymerization, the excess gas was discharged and the contents were taken out by cooling to obtain 123 g of white polymer. Catalytic efficiency is 83
It was Kg / gZr. The density of the obtained polymer is 0.9170 g /
cm ³ , melting point 118.2 ° C, MI 1.2g / 10min, Mw / Mn 6.
It was 7. Example 3 (1) Preparation of transition metal catalyst component Under nitrogen, 150 ml of purified toluene was added to a 300 ml three-necked flask equipped with an electromagnetic induction stirrer, 3.8 g of tetrabenzylzirconium and 2.6 g of cyclopentadiene were added, and the mixture was allowed to stand at room temperature.
After stirring for a minute, the system was kept at 0 ° C., 1.3 g of lithium aluminum triethoxyhydride was added dropwise, and after completion of the addition, the system was stirred at room temperature for 4 hours to prepare a transition metal catalyst component. The concentration of this solution is 0.06 mmol / ml as Zr. (2) Contact of transition metal catalyst component with promoter 3 ml of the above solution was sampled in a 50 ml flask, 3.6 ml of a toluene solution of methylaluminoxane (concentration 1 mmol / ml) was added, and the mixture was stirred at room temperature for 30 minutes. (3) Polymerization A 3 L capacity stainless steel autoclave equipped with a stirrer was purged with nitrogen, and 1 liter of purified toluene was added thereto, and the mixture obtained in (2) above was used as Zr to give 2 mg.
Was added, 0.05 mmol of ferrocenium tetra (pentafluorophenyl) borate was further added, the system was heated to 60 ° C., and a mixed gas of ethylene and butene-1 (butene-1 /
Polymerization was initiated by injecting ethylene molar ratio of 0.25) so as to be 9 Kgf / cm ² G, and the total pressure was adjusted while continuously supplying a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio of 0.05). Polymerization was carried out for 2 hours while maintaining at 9 Kgf / cm ² G. After the polymerization was completed, the excess gas was discharged, the contents were cooled and the contents were taken out to obtain 50 g of a white polymer. Catalyst efficiency is 25
It was Kg / gZr. The density of the obtained polymer is 0.9150 g /
cm3, melting point 114.2 ° C, MI 1.3g / 10min, Mw / Mn 6.
It was 2. Example 4 (1) Preparation of catalyst 150 ml of purified toluene was added to a 300 ml three-necked flask equipped with an electromagnetic induction stirrer under nitrogen, 3.1 g of dibutoxydichlorozirconium and 9.2 g of indene were added, and the mixture was stirred at room temperature for 30 minutes,
Lithium aluminum hydride by keeping the system at 0 ℃
9.1 g was added, and the mixture was brought to room temperature and stirred for 24 hours. The obtained slurry was sampled in a 50 ml flask as zirconium so as to have 0.2 mmol atom, 4 ml of a toluene solution of methylaluminoxane (concentration 1 mmol / ml) was added, and the mixture was stirred at room temperature for 30 minutes. Then Anilinium 1-carbadodecaborate
0.2 mmol was added and stirred at room temperature for 3 hours to obtain a catalyst. (2) Polymerization The same procedure as in Example 1 was carried out, except that the catalyst obtained in (1) above was treated with Zr.
0.5 mg was added to carry out polymerization. The amount of the polymer obtained was 15 g, and the catalyst efficiency was 30 kg / gZr. Polymer density is 0.9250g / cm ³ , melting point is 119.7 ℃, MI is 7.1g / 10m
The in and Mw / Mn were 6.7. Example 5 (1) Preparation of catalyst Under nitrogen, 150 ml of purified toluene was added to a 300 ml three-necked flask equipped with an electromagnetic induction stirrer, and then 3.5 g of tributoxychlorozirconium and trimethylsilylcyclopentadiene 11 were added.
g was added, the mixture was stirred at room temperature for 30 minutes, 3.2 g of aluminum hydride was added while maintaining the system at 0 ° C., and the mixture was stirred at room temperature for 24 hours.
The resulting solution was added to a 50 ml flask as zirconium 0.2
It was collected so as to have mmol atoms, 4 ml of a toluene solution of methylaluminoxane (concentration 1 mmol / ml) was added, and the mixture was stirred at room temperature for 30 minutes. Then, 0.2 mmol of tributylammonium bis (nonahydro-1,3-dicarbaunaborate) cobaltate (III) was added and stirred at room temperature for 3 hours to obtain a catalyst. (2) Polymerization The same procedure as in Example 4 was performed. The obtained polymer was 10 g, and the catalyst efficiency was 20 kg / gZr. The density of the polymer is
0.9105g / cm ³ , melting point 111.2 ° C, MI 1.4g / 10mi
n and Mw / Mn were 7.3. Example 6 (1) Preparation of catalyst 150 ml of purified toluene was added to a 300 ml three-necked flask equipped with an electromagnetic induction stirrer under nitrogen, 4.2 g of tetrabutoxyzirconium and 7.5 g of 1,3 dimethylcyclopentadiene were added, and the mixture was stirred at room temperature for 30 minutes, The system was maintained at 0 ° C., 9.1 g of diisobutylaluminum hydride was added dropwise, and after completion of the addition, the system was brought to room temperature and stirred for 24 hours. The obtained solution was sampled as zirconium in a 50 ml flask so that the concentration of zirconium could be 0.2 mmol, 4 ml of a toluene solution of methylaluminoxane (concentration 1 mmol / ml) was added, and the mixture was stirred at room temperature for 30 minutes. Then trityl tetra (pentafluorophenyl) borate 0.
2 mmol was added and stirred at room temperature for 3 hours to obtain a catalyst. (2) Polymerization The same procedure as in Example 4 was performed. The obtained polymer was 200 g, and the catalyst efficiency was 400 kg / gZr. Polymer density is 0.9150g / cm ³ , melting point is 114.5 ℃, MI is 0.9g / 10min, Mw
/ Mn was 7.4. Example 7 (1) Preparation of catalyst 150 ml of purified toluene was added to a 300 ml three-necked flask equipped with an electromagnetic induction stirrer under nitrogen, 2.3 g of hafnium tetrachloride and 4.7 g of indene were added, and the mixture was stirred at room temperature for 30 minutes, and then the system was heated to 0 ° C. While maintaining, 11.4 g of sodium borohydride was added, and the mixture was brought to room temperature and stirred for 24 hours. The resulting solution was sampled in a 50 ml flask as zirnium so as to have 0.2 mmol atom,
0.2 mmol of trityl-1-carbaundecaborate was added and stirred at room temperature for 3 hours. Then, 4 ml of a toluene solution of methylaluminoxane (concentration 1 mmol / ml) was added and the mixture was stirred at room temperature for 3
After stirring for 0 minutes, a catalyst was obtained. (2) Polymerization The same procedure as in Example 4 was performed. The obtained polymer was 10 g, and the catalyst efficiency was 20 kg / gHf. The density of the polymer is
0.9200g / cm ³ , melting point 118.5 ℃, MI 2.5g / 10min, Mw / M
n was 7.2. Example 8 (1) Preparation of catalyst Under nitrogen, 150 ml of purified toluene was added to a 300 ml three-necked flask equipped with an electromagnetic induction stirrer, then 3.4 g of tetrabutoxytitanium and 5.3 g of cyclopentadiene were added, and the mixture was stirred at room temperature for 30 minutes and then heated to 0 ° C. 22.5 g of diisobutylaluminum hydride was added while maintaining the temperature of
Stir for hours. The resulting solution was sampled in a 50 ml flask as titanium so as to have 0.2 mmol atom, and 4 ml of a toluene solution of methylaluminoxane (concentration 1 mmol / ml) was prepared.
Was added and the mixture was stirred at room temperature for 30 minutes. Then, 0.2 mmol of tri (pentafluorophenyl) borane was added and stirred at room temperature for 3 hours to obtain a catalyst. (2) Polymerization The same procedure as in Example 4 was performed. The obtained polymer was 95 g, and the catalyst efficiency was 190 kg / gTi. Polymer density is 0.9250g / cm ³ , melting point is 118.7 ℃, MI is 1.3g / 10min, Mw
/ Mn was 6.9. Example 9 (1) Preparation of catalyst Under nitrogen, 150 ml of purified toluene was added to a 300 ml three-necked flask equipped with an electromagnetic induction stirrer, 4.1 g of tetrapropylhafnium and 5.3 g of cyclopentadiene were added, and the mixture was stirred at room temperature for 30 minutes and then heated to 0 ° C. 5.8 g of zinc borohydride was added while holding the mixture, and the mixture was stirred at room temperature for 24 hours. 50 ml of the obtained solution
Hafnium was collected in a flask so as to have a concentration of 0.2 mmol atom, 4 ml of a toluene solution of methylaluminoxane (concentration 1 mmol / ml) was added, and the mixture was stirred at room temperature for 30 minutes. Then ferrocenium-2.9-dicarbaundecaborate
0.2 mmol was added and stirred at room temperature for 3 hours to obtain a catalyst. (2) Polymerization The same procedure as in Example 4 was performed. The obtained polymer was 10 g, and the catalyst efficiency was 20 kg / gHf. The density of the polymer is
0.9250g / cm ³ , melting point 117.9 ℃, MI 0.3g / 10min, Mw / M
n was 7.2. Example 10 (1) Preparation of catalyst 150 ml of purified toluene was added to a 300 ml three-necked flask equipped with an electromagnetic induction stirrer under nitrogen, 2.3 g of tetrachlorozirconium and 6.5 g of methylcyclopentadiene were added, and the mixture was allowed to stand at room temperature 30
After stirring for a minute, the system was kept at 0 ° C. and 9.1 g of diisobutylaluminum hydride was added dropwise. After completion of the addition, the system was brought to room temperature and stirred for 24 hours. The resulting solution was sampled in a 50 ml flask as zirconium to have 0.2 mmol atom,
Toluene solution of methylaluminoxane (concentration 1 mmol / m
l) 4 ml was added, and the mixture was stirred at room temperature for 30 minutes. Then, 0.2 mmol of trityl-bis (nonahydride-1,3-dicarbaunaborate) cobaltate (III) was added and stirred at room temperature for 3 hours to obtain a catalyst. (2) Polymerization The same procedure as in Example 4 was performed. The obtained polymer was 80 g, and the catalyst efficiency was 160 kg / gZr. Polymer density is 0.9200g / cm ³ , melting point is 115.1 ℃, MI is 8.3g / 10min, Mw
/ Mn was 7.5. Example 11 (1) Preparation of catalyst To a 300 ml three-necked flask equipped with an electromagnetic induction stirrer, 150 ml of purified toluene was added under nitrogen, then 3.3 g of tetrapropoxyzirconium and 9.2 g of indene were added, and the mixture was stirred at room temperature for 30 minutes, and then 0
The system was kept at 0 ° C., 9.3 g of diisobutylaluminum hydride was added, and after the addition was completed, the system was brought to room temperature and stirred for 24 hours. The resulting solution was sampled in a 50 ml flask as zirconium so that the amount of zirconium was 0.2 mmol atom, 10 ml of a toluene solution of methylaluminoxane (concentration 1 mmol / ml) was added, and the mixture was stirred at room temperature for 30 minutes. Next, 0.2 mmol of ferrocenium bis (undecahydrido-7.8-dicarbaundecaborate) nickelate (III) was added and stirred at room temperature for 3 hours to obtain a catalyst. (2) Polymerization The same procedure as in Example 4 was performed. The polymer obtained was 100 g, and the catalyst efficiency was 200 kg / g Zr. Polymer density is 0.9105g / cm ³ , melting point is 114.3 ℃, MI is 1.3g / 10min, Mw
/ Mn was 8.5. Example 12 (1) Preparation of catalyst 150 ml of purified toluene was added to a 300 ml three-necked flask equipped with an electromagnetic induction stirrer under nitrogen, and then 3.3 g of tetrapropoxyzirconium and 9.3 g of bisindenylethane were added to the mixture at room temperature 30
After stirring for a minute, the system was kept at 0 ° C. and 9.1 g of diisobutylaluminum hydride was added dropwise over 30 minutes. After completion of the dropping, the system was brought to room temperature and stirred for 24 hours. The concentration of this solution is Zr
Is 0.058 mmol / ml. Solution 3 above in a 50 ml flask
Take ml to collect methylaluminoxane (concentration 1 mmol / ml)
4.4 ml of a toluene solution of was added, and the mixture was stirred at room temperature for 30 minutes. Then, 0.2 mmol of triethylammonium tetra (o-fluorophenyl) borate was added and stirred at room temperature for 3 hours to obtain a catalyst. (2) Polymerization A 3 L stainless steel autoclave equipped with a stirrer was replaced with nitrogen, and 1 liter of purified toluene was added to the autoclave, and the catalyst obtained in (1) above was used as Zr.
mmg was added, the system was heated to 60 ° C, and ethylene was added at 9 kgf / cm ²
Polymerization was started by injecting so as to give G, and while continuously feeding ethylene, polymerization was carried out for 2 hours while maintaining the total pressure at 9 kgf / cm ² G. After the polymerization was completed, the excess gas was discharged, the contents were cooled and the contents were taken out to obtain 40 g of a white polymer. The catalyst efficiency was 20 kg / gZr. Polymer density is 0.9510
g / cm ³ , melting point 132 ° C., MI 3.5 g / 10 min, Mw / Mn 6.3. Comparative Example 1 The procedure of Example 1 was repeated except that catechol borane was not used. The catalyst efficiency is 0.3 kg / g Zr, the density of the obtained polymer is 0.9250 g / cm ³ , the melting point is 119.5 ° C, and the MI is 1.3 g.
It was / 10 min. Comparative Example 2 The procedure of Example 1 was repeated except that indene was not used. The catalyst efficiency was 0.003 kg / gZr, and the melting point of the obtained polymer was 123.5 ° C. Comparative Example 3 The procedure of Example 1 was repeated, except that triethylammonium tetra (pentafluorophenyl) borate was not used. The catalyst efficiency is 5 kg / gZr, the density of the obtained polymer is 0.9200 g / cm ³ , the melting point is 118.5 ° C, and the MI is 2.3 g / 10 min.
Met. Comparative Example 4 Example 8 was repeated except that tri (pentafluorophenyl) borane was not used. Catalyst efficiency is 0.005kg /
It was gZr.

[Brief description of drawings]

FIG. 1 is a flow chart showing steps for preparing a catalyst used in the present invention.

Claims (3)

[Claims] 1. An olefin polymerization catalyst obtained by bringing the following components (A) to (D) into contact with each other. (A) A compound represented by the general formula Me ¹ (OR ¹ ) _p R ² _q X ¹ _4-pq [In the formula, R ¹ and R ² are independently a hydrocarbon group having 1 to 24 carbon atoms, and X ¹ is Halogen atom, Me ¹ is Ti, Zr or Hf
, P is 0 ≦ p ≦ 4, q is 0 ≦ q ≦ 4, and p + q is 0.
≦ p + q ≦ 4. ] (B) At least one kind of metal hydride compounds represented by the following (a) to (c) (a) Me ² H _a R ³ _3-a (b) Me ³ [Me ² H _b R ⁴ _c (OR ⁵ ) _4-bc ] _z (c) _Formula 1 [Formula 1] [In the formula, R ³ , R ⁴ , R ⁵ and R 6 each independently have 1 to 2 carbon atoms.
4, a hydrocarbon group of 4, Me ² is an element of Group 13 of the periodic table, Me ³ is an element of Group 1, 2 or 12 of the periodic table, z is the valence of Me ³ , a, b, c and d
Are 1 ≦ a ≦ 3, 1 ≦ b ≦ 4, 0 ≦ c ≦ 3, 0 ≦ d, respectively.
≦ 4, and 1 ≦ b + c ≦ 4. ] (C) Organic cyclic compound having two or more conjugated double bonds (D) Borate and / or borane 2. An olefin polymerization catalyst obtained by bringing the following components (A) to (E) into contact with each other. (A) A compound represented by the general formula Me ¹ (OR ¹ ) _p R ² _q X ¹ _4-pq [In the formula, R ¹ and R ² are independently a hydrocarbon group having 1 to 24 carbon atoms, and X ¹ is Halogen atom, Me ¹ is Ti, Zr or Hf
, P is 0 ≦ p ≦ 4, q is 0 ≦ q ≦ 4, and p + q is 0.
≦ p + q ≦ 4. ] (B) At least one kind of metal hydride compounds represented by the following (a) to (c) (a) Me ² H _a R ³ _3-a (b) Me ³ [Me ² H _b R ⁴ _c (OR ⁵ ) _4-bc ] _z (c) _Formula 2 [Formula 2] [In the formula, R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a carbon number of 1 to 2;
4, a hydrocarbon group of 4, Me ² is an element of Group 13 of the periodic table, Me ³ is an element of Group 1, 2 or 12 of the periodic table, z is the valence of Me ³ , a, b, c and d
Respectively 0 <a ≦ 3, 1 ≦ b ≦ 4, 0 ≦ c ≦ 3, 0 ≦ d
≦ 4, and 1 ≦ b + c ≦ 4. ] (C) Organic cyclic compound having two or more conjugated double bonds (D) Borate and / or borane (E) Modified organoaluminum compound containing Al-O-Al bond 3. A method for producing an olefin polymer, which comprises polymerizing or copolymerizing an olefin in the presence of the catalyst according to claim 1.